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DOI: 10.1039/A708852C (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1998, 1047-1058

Axially chiral cyclopentadienyl ligands: stereoselective synthesis of 1-substituted-9-(1′-naphthyl)fluorenes and retention of axial chirality in the fluorenyl carbanions[hair space]1

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Robert W. Baker, Michael A. Foulkes and James A. Taylor

Abstract

1-(tert-Butyl- or 1-([hair space]p-tolyl-sulfinyl)naphthalene-2-carboxylate esters undergo coupling reactions with fluorenyllithiums substituted at the 1-position, providing 1-(1′-substituted-fluoren-9′-yl)naphthalene-2-carboxylate esters as single rotamers where the naphthalene ester substituent is syn to the fluorene 9-H. The stereoselectivity of the coupling reaction, with respect to asymmetric induction at the fluorene 9-C, varies from 21–95% (ee or de) dependant on the sulfoxide, ester and fluorene substituents, and the reaction temperature. The stereomutation of +ac[hair space](R)-1-methyl-9-(2′-methoxymethyl-1′-naphthyl)fluorene 33 into ent-33 was achieved through thermal atropisomerisation of 33 to the –sc[hair space](R)-rotamer 34, followed by lithiation of 34 and then reprotonation of the resultant fluorenyllithium 35, demonstrating the retention of axial chirality in the fluorenyl carbanion.

References

  1. Preliminary communication: R. W. Baker, T. W. Hambley and P. Turner, J. Chem. Soc., Chem. Commun., 1995, 2509 Search PubMed.
  2. R. L. Halterman, Chem. Rev., 1992, 92, 965 CrossRef CAS.
  3. A. H. Hoveyda and J. P. Morken, Angew. Chem., Int. Ed. Engl., 1996, 35, 1262 Search PubMed.
  4. H.-H. Brintzinger, D. Fisher, R. Mülhaupt, B. Rieger and R. M. Waymouth, Angew. Chem., Int. Ed. Engl., 1995, 34, 1143 Search PubMed.
  5. R. D. Broene and S. L. Buchwald, J. Am. Chem. Soc., 1993, 115, 12 569 CrossRef CAS.
  6. C. A. Willoughby and S. L. Buchwald, J. Am. Chem. Soc., 1994, 116, 11 703 CrossRef CAS.
  7. M. B. Carter, B. Schiøtt, A. Gutiérrez and S. L. Buchwald, J. Am. Chem. Soc., 1994, 116, 11 667 CrossRef CAS.
  8. J. P. Morken, M. T. Didiuk and A. H. Hoveyda, J. Am. Chem. Soc., 1993, 115, 6997 CrossRef CAS.
  9. J. B. Jaquith, J. Guan, S. Wang and S. Collins, Organometallics, 1995, 14, 1079 CrossRef CAS.
  10. F. R. W. P. Wild, L. Zsolnai, G. Huttner and H.-H. Brintzinger, J. Organmet. Chem., 1982, 232, 233 Search PubMed.
  11. J. P. Mitchell, S. Hajela, S. K. Brookhart, K. L. Hardcastle, L. M. Henling and J. E. Bercaw, J. Am. Chem. Soc., 1996, 118, 1045 CrossRef CAS.
  12. M. A. Giardello, V. P. Conticello, L. Brard, M. Sabat, A. L. Rheingold, C. L. Stern and T. J. Marks, J. Am. Chem. Soc., 1994, 116, 10 212 CrossRef CAS.
  13. M. A. Giardello, M. S. Eisen, C. L. Stern and T. J. Marks, J. Am. Chem. Soc., 1995, 117, 12 114 CrossRef CAS.
  14. R. B. Grossman, J.-C. Tsai, W. M. Davis, A. Gutiérrez and S. L. Buchwald, Organometallics, 1994, 13, 3892 CrossRef CAS.
  15. M. A. Giardello, V. P. Conticello, L. Brard, M. R. Gagné and T. J. Marks, J. Am. Chem. Soc., 1994, 116, 10 241 CrossRef CAS.
  16. R. L. Halterman and T. M. Ramsey, Organometallics, 1993, 12, 2879 CrossRef CAS.
  17. W. E. Ellis, T. K. Hollis, W. Odenkirk, J. Whelan, R. Ostrander, A. L. Rheingold and B. Bosnich, Organometallics, 1993, 12, 4391 CrossRef CAS.
  18. J. Okuda, Comments Inorg. Chem., 1994, 16, 185 CAS.
  19. C. Lensink, Tetrahedron: Asymmetry, 1995, 6, 2033 CrossRef CAS.
  20. J. Christoffers and R. G. Bergman, Angew. Chem., Int. Ed. Engl., 1995, 34, 2266 Search PubMed.
  21. Y. Nishibayashi, I. Takei and N. Hidai, Organometallics, 1997, 16, 3091 CrossRef CAS.
  22. E. A. Chandross and C. F. Sheley, J. Am. Chem. Soc., 1968, 90, 4345 CrossRef CAS.
  23. M. Ōki, Top. Stereochem., 1983, 14, 1 Search PubMed and references therein.
  24. M. Ōki, The Chemistry of Rotational Isomers, Springer-Verlag, Berlin, 1993, and references therein Search PubMed.
  25. M. Nakamura and M. Ōki, Chem. Lett., 1975, 671 CAS.
  26. M. Nakamura, Y. Suzuki and M. Ōki, Bull. Chem. Soc. Jpn., 1985, 58, 2370 CAS.
  27. Ref. 24, p. 119.
  28. R. W. Baker, D. C. R. Hockless, G. R. Pocock, M. V. Sargent, B. W. Skelton, A. M. Sobolev, E. Twiss and A. H. White, J. Chem. Soc., Perkin Trans. 1, 1995, 2615 RSC.
  29. R. Saito and M. Ōki, Bull. Chem. Soc. Jpn., 1982, 55, 3273 CAS.
  30. D. J. Cram, Fundamentals of Carbanion Chemistry, Academic Press, New York, 1965, ch. 3 Search PubMed.
  31. S. Gronert and A. Streitwieser, Jr., J. Am. Chem. Soc., 1988, 110, 2836 CrossRef CAS.
  32. R. W. Baker, T. W. Hambley, P. Turner and B. J. Wallace, Chem. Commun., 1996, 2571 RSC (Corrigendum, 1997, 506).
  33. K. K. Andersen, W. Gaffield, N. E. Papanikolaou, J. W. Foleyt and R. I. Perkins, J. Am. Chem. Soc., 1964, 86, 5637 CrossRef CAS.
  34. J. M. Klunder and K. B. Sharpless, J. Org. Chem., 1987, 52, 2598 CrossRef CAS.
  35. M. C. Kloetzel and H. E. Mertel, J. Am. Chem. Soc., 1950, 72, 4786 CrossRef CAS.
  36. J. F. Cairns and W. K. Hickinbottom, J. Chem. Soc., 1962, 867 RSC.
  37. N. Campbell and N. H. Wilson, J. Chem. Soc., Perkin Trans. 1, 1972, 2739 RSC.
  38. E. K. Weisburger and J. H. Weisburger, J. Org. Chem., 1953, 18, 864 CrossRef CAS.
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